CN104607162A - Cation exchange chimeric cryogel separation medium and preparation method thereof - Google Patents

Cation exchange chimeric cryogel separation medium and preparation method thereof Download PDF

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Publication number
CN104607162A
CN104607162A CN201510019873.1A CN201510019873A CN104607162A CN 104607162 A CN104607162 A CN 104607162A CN 201510019873 A CN201510019873 A CN 201510019873A CN 104607162 A CN104607162 A CN 104607162A
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medium
cation exchange
mosaic type
cryogel
brilliant
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CN104607162B (en
Inventor
贠军贤
姚善泾
林东强
沈绍传
姚克俭
潘毛毛
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
    • B01J20/285—Porous sorbents based on polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/44—Materials comprising a mixture of organic materials
    • B01J2220/445—Materials comprising a mixture of organic materials comprising a mixture of polymers

Abstract

The invention discloses a cation exchange chimeric cryogel separation medium and a preparation method thereof. The cation exchange chimeric cryogel separation medium is characterized in that the chimeric cryogel medium is obtained from grafting and modifying a poly hydroxyethyl methacrylate continuous bed medium with internally chimeric cellulose microspheres through 2-acrylamide-2-methyl-1-propanesulfonic acid, a pore diameter of the chimeric cryogel medium ranges from 0.1 mu m to 300 mu m, the porosity is 80%-95%, the chimeric cryogel medium has a sulfonic group cation exchange functional group, and the adsorption capacity of cryogel for lysozyme model protein is 1-5mg/mL. The pore diameter of the chimeric cryogel medium ranges from sub-micron dimension to micron dimension, the cryogel medium has multi-level pores including diffusion mass transfer small pores and convective mass transfer ultra-large pores, and accordingly, the specific surface area of the cryogel medium and adsorption sites after chemical modification are increased; meanwhile, a matrix material of the cryogel medium has good biocompatibility, is stable in a separation environment, can be repeatedly used, has good safety and has wide application prospect in the biochemical separation field.

Description

Brilliant glue separating medium of a kind of cation exchange mosaic type and preparation method thereof
Technical field
The invention belongs to chemical separating media technology field, be specifically related to brilliant glue separating medium of a kind of cation exchange mosaic type and preparation method thereof.
Background technology
Crystal gel medium is the novel chromatography medium of one occurred in recent years, there is size from the super large hole of several microns to hundreds of microns in its medium skeleton, microbial cell or cell fragment is allowed to pass through smoothly, therefore, be suitable for from microbial fermentation solution, cell culture fluid, blood and the complex biological feed liquid fluid containing other solid phase impurity as quick separating large biological molecule material whey, cow's milk etc.Its separation process step is few, and the mass transfer of large biological molecule in brilliant glue column is rapid, and be separated consuming time short, separative efficiency is good, has important application prospect in bio-separation field.
Although Chinese scholars has been successfully prepared the crystal gel medium of different series, but, existing crystal gel medium pore-size size mainly concentrates on several microns to about 100 ~ 200 microns, specific area is less, pore-level is secondary single, adsorption site is less, and the adsorption capacity of crystal gel medium and separating effect are not all given full play to.But, the crystal gel medium of multistage secondary aperture will be prepared by conventional crystallization pore and polymerisation coupling process, then more difficult.Meanwhile, the brilliant glue mosaic type composite crystal glue medium with cation exchange functional group does not then have bibliographical information.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the invention is to provide brilliant glue separating medium of a kind of cation exchange mosaic type and preparation method thereof.
The brilliant glue separating medium of described a kind of cation exchange mosaic type, it is characterized in that described mosaic type crystal gel medium is continuous bed medium, there is the multilevel hole of aperture from sub-micron and micron dimension, described mosaic type crystal gel medium is embedded with brilliant glue microballoon, and with such as formula the sulfonic group cation exchange functional group shown in (I):
（Ⅰ）
The brilliant glue separating medium of described a kind of cation exchange mosaic type, is characterized in that the matrix of described mosaic type crystal gel medium adopts the brilliant gel matrix of the poly hydroxy ethyl acrylate of embedded cellulose microsphere.
The brilliant glue separating medium of described a kind of cation exchange mosaic type, is characterized in that the aperture of described mosaic type crystal gel medium multilevel hole is 0.1 ~ 300 μm, porosity 80 ~ 95%, is the brilliant glue of 1 ~ 5 mg/mL to the adsorption capacity of lysozyme model protein.
The preparation method of the brilliant glue separating medium of described cation exchange mosaic type, it is characterized in that described preparation method is as follows: with the monomer that can react with the brilliant gel matrix of the poly hydroxy ethyl acrylate mosaic type of embedded cellulose microsphere with ethylene linkage and sulfonic acid group for grafted monomers, with Cu 3+solion is catalyst, and carry out grafting and modifying to the brilliant gel matrix of the poly hydroxy ethyl acrylate mosaic type of embedded cellulose microsphere, immobilized sulfonic group cation exchange functional group in brilliant glue skeleton, obtains described cation exchange mosaic type crystal gel medium.
The preparation method of the brilliant glue separating medium of described cation exchange mosaic type, it is characterized in that described grafted monomers is 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid, described grafted monomers adds with the form of 0.5 ~ 2 M monomer solution, and the volumetric usage of described monomer solution is 3 ~ 5 times of mosaic type brilliant glue continuous bed dielectric matrix volume.
The preparation method of the brilliant glue separating medium of described cation exchange mosaic type, is characterized in that described Catalysts Cu 3+the final concentration of solion is 0.03 ~ 0.06M, and volumetric usage is 3 ~ 5 times of mosaic type brilliant glue continuous bed dielectric matrix volume.
The preparation method of the brilliant glue separating medium of described cation exchange mosaic type, it is characterized in that the temperature of described graft reaction is 45 ~ 55 DEG C, the reaction time is 0.5 ~ 4h.
The preparation method of the brilliant glue separating medium of described cation exchange mosaic type, is characterized in that described Cu 3+solion is K 5[Cu (HIO 6) 2] solution or Na 5[Cu (HIO 6) 2] solution.
By adopting above-mentioned technology, the present invention has following beneficial effect:
1) host material of mosaic type crystal gel medium provided by the invention is natural or polymeric material that the is clinical and good biocompatibility of extensive use in medical diagnosis, as with ethylene linkage and sulfonic acid group can gel matrix brilliant in the poly hydroxy ethyl acrylate mosaic type of embedded cellulose microsphere, its biocompatibility is excellent, very stable under isolating environment, can reuse, there is good security;
2) the brilliant glue fiber element of mosaic type provided by the invention is embedded in poly hydroxy ethyl acrylate with porous microsphere form, different from other cation exchange crystal gel medium existing, which forms and possess diffusion mass transfer absorption aperture and the multilevel hole of convective mass transfer super big hole simultaneously, improve the adsorption site after the specific area of crystal gel medium and chemical modification;
3) the brilliant glue separating medium of mosaic type of the present invention, its preparation method is simple, easy to operate, is suitable in the application of bio-chemistry separation field, and has broad application prospects in bio-chemistry separation field.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
embodiment 1
With the Na that 15.7mL concentration is 0.037M 5[Cu (HIO 6) 2] solution is catalyst, the brilliant gel matrix of embedded cellulose microsphere poly hydroxy ethyl acrylate mosaic type of cut-off footpath 10 mm, height 40 mm, the brilliant glue microspherulite diameter 300 ~ 1900 μm of its embedded cellulose, average grain diameter about 900 μm, the mass ratio accounting for brilliant gel matrix skeleton is 25%; At 45 DEG C, graft reaction 4 h is carried out to brilliant gel matrix with 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid aqueous solution that 15.7 mL concentration are 0.5 M, obtain poly hydroxy ethyl acrylate matrix and cellulose base cation exchange mosaic type crystal gel medium, its effective drainage porosity 84%, maximum pore rate 95%, about 0.1 ~ 300 μm, aperture, to adsorption capacity 1.10 mg/mL of lysozyme model protein.
embodiment 2
With the K that 9 mL concentration are 0.06M 5[Cu (HIO 6) 2solution is catalyst, the brilliant gel matrix of embedded cellulose microsphere poly hydroxy ethyl acrylate mosaic type of cut-off footpath 10 mm, height 38 mm, the brilliant glue microspherulite diameter 300 ~ 1900 μm of its embedded cellulose, average grain diameter about 900 μm, the mass ratio accounting for brilliant gel matrix skeleton is 25%; At 55 DEG C, graft reaction 0.5 h is carried out to brilliant gel matrix with 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid aqueous solution that 9 mL concentration are 2 M, obtain poly hydroxy ethyl acrylate matrix and cellulose base cation exchange mosaic type crystal gel medium, its effective drainage porosity 83 %, maximum pore rate 94 %, pore size about 0.1 ~ 300 μm, to saturated adsorption capacity 5 mg/mL of lysozyme model protein.
embodiment 3
With the K that 30 mL concentration are 0.04M 5[Cu (HIO 6) 2solution is catalyst, the brilliant gel matrix of embedded cellulose microsphere poly hydroxy ethyl acrylate mosaic type of cut-off footpath 10 mm, height 52 mm, the brilliant glue microspherulite diameter 300 ~ 1900 μm of its embedded cellulose, average grain diameter about 900 μm, the mass ratio accounting for brilliant gel matrix skeleton is 30%; At 51 DEG C, graft reaction 2 h is carried out to brilliant gel matrix with 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid aqueous solution that 20 mL concentration are 1 M, obtain poly hydroxy ethyl acrylate matrix and cellulose base cation exchange mosaic type crystal gel medium, its effective drainage porosity 80%, maximum pore rate 94%, pore size about 0.1 ~ 270 μm, to adsorption capacity 3.4 mg/mL of lysozyme model protein.
embodiment 4
With the Na that 20 mL concentration are 0.03M 5[Cu (HIO 6) 2] solution is catalyst, the brilliant gel matrix of embedded cellulose microsphere poly hydroxy ethyl acrylate mosaic type of cut-off footpath 10 mm, height 40 mm, the brilliant glue microspherulite diameter 300 ~ 1900 μm of its embedded cellulose, average grain diameter about 900 μm, the mass ratio accounting for brilliant gel matrix skeleton is 25%; At 52 DEG C, graft reaction 2 h is carried out to brilliant gel matrix with 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid aqueous solution that 17 mL concentration are 0.5 M, obtain poly hydroxy ethyl acrylate matrix and cellulose base cation exchange mosaic type crystal gel medium, its effective drainage porosity 85%, maximum pore rate 95%, about 0.1 ~ 300 μm, aperture, to adsorption capacity 1 mg/mL of lysozyme model protein.
embodiment 5
With the Na that 30 mL concentration are 0.04M 5[Cu (HIO 6) 2] solution is catalyst, the brilliant gel matrix of embedded cellulose microsphere poly hydroxy ethyl acrylate mosaic type of cut-off footpath 10 mm, height 50 mm, the brilliant glue microspherulite diameter 300 ~ 1900 μm of its embedded cellulose, average grain diameter about 900 μm, the mass ratio accounting for brilliant gel matrix skeleton is 25%; At 48 DEG C, graft reaction 1.8 h is carried out to brilliant gel matrix with 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid aqueous solution that 20 mL concentration are 1.8 M, obtain poly hydroxy ethyl acrylate matrix and cellulose base cation exchange mosaic type crystal gel medium, its effective drainage porosity 85%, maximum pore rate 95%, about 0.1 ~ 300 μm, aperture, to adsorption capacity 3.6 mg/mL of lysozyme model protein.

Claims (8)

1. the brilliant glue separating medium of cation exchange mosaic type, it is characterized in that described mosaic type crystal gel medium is continuous bed medium, there is the multilevel hole of aperture from sub-micron and micron dimension, described mosaic type crystal gel medium is embedded with brilliant glue microballoon, and with such as formula the sulfonic group cation exchange functional group shown in (I):
（Ⅰ）。
2. the brilliant glue separating medium of a kind of cation exchange mosaic type according to claim 1, is characterized in that the matrix of described mosaic type crystal gel medium adopts the brilliant gel matrix of the poly hydroxy ethyl acrylate of embedded cellulose microsphere.
3. the brilliant glue separating medium of a kind of cation exchange mosaic type according to claim 1, the aperture that it is characterized in that described mosaic type crystal gel medium multilevel hole is 0.1 ~ 300 μm, porosity 80 ~ 95% is the brilliant glue of 1 ~ 5 mg/mL to the adsorption capacity of lysozyme model protein.
4. the preparation method of the brilliant glue separating medium of cation exchange mosaic type according to claim 1, it is characterized in that described preparation method is as follows: with the monomer that can react with the brilliant gel matrix of the poly hydroxy ethyl acrylate mosaic type of embedded cellulose microsphere with ethylene linkage and sulfonic acid group for grafted monomers, with Cu 3+solion is catalyst, and carry out grafting and modifying to the brilliant gel matrix of the poly hydroxy ethyl acrylate mosaic type of embedded cellulose microsphere, immobilized sulfonic group cation exchange functional group in brilliant glue skeleton, obtains described cation exchange mosaic type crystal gel medium.
5. the preparation method of the brilliant glue separating medium of cation exchange mosaic type according to claim 4, it is characterized in that described grafted monomers is 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid, described grafted monomers adds with the form of 0.5 ~ 2 M monomer solution, and the volumetric usage of described monomer solution is 3 ~ 5 times of mosaic type brilliant glue continuous bed dielectric matrix volume.
6. the preparation method of the brilliant glue separating medium of cation exchange mosaic type according to claim 4, is characterized in that described Catalysts Cu 3+the final concentration of solion is 0.03 ~ 0.06M, and volumetric usage is 3 ~ 5 times of mosaic type brilliant glue continuous bed dielectric matrix volume.
7. the preparation method of the brilliant glue separating medium of cation exchange mosaic type according to claim 4, it is characterized in that the temperature of described graft reaction is 45 ~ 55 DEG C, the reaction time is 0.5 ~ 4h.
8. the preparation method of the brilliant glue separating medium of cation exchange mosaic type according to claim 4, is characterized in that described Cu 3+solion is K 5[Cu (HIO 6) 2] solution or Na 5[Cu (HIO 6) 2] solution.
CN201510019873.1A 2015-01-15 2015-01-15 A kind of cation exchange mosaic type crystalline substance glue separating medium and preparation method thereof Active CN104607162B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106632860A (en) * 2016-12-23 2017-05-10 浙江工业大学 Glucosan-based cryogel microsphere separating medium and preparation method thereof
CN107141403A (en) * 2017-05-16 2017-09-08 齐鲁工业大学 A kind of Cu2+Chelate the preparation method of polyhydroxypropyl methaciylate super-macroporous crystal gel medium

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CN1903438A (en) * 2006-07-12 2007-01-31 浙江工业大学 Cation exchange type super macroporous continous bed crystal gel medium and its prepn. method
CN101081373A (en) * 2007-06-29 2007-12-05 浙江工业大学 Cation-exchange crystal glue chromatography medium and method for preparing the same
CN103230784A (en) * 2013-04-26 2013-08-07 浙江工业大学 Composite continuous bed cryogel and preparation thereof, and application in separating IgG and albumin
CN103252218A (en) * 2013-04-26 2013-08-21 浙江工业大学 Hybrid overall crystal gel medium and preparation method thereof

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Publication number Priority date Publication date Assignee Title
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CN1903438A (en) * 2006-07-12 2007-01-31 浙江工业大学 Cation exchange type super macroporous continous bed crystal gel medium and its prepn. method
CN101081373A (en) * 2007-06-29 2007-12-05 浙江工业大学 Cation-exchange crystal glue chromatography medium and method for preparing the same
CN103230784A (en) * 2013-04-26 2013-08-07 浙江工业大学 Composite continuous bed cryogel and preparation thereof, and application in separating IgG and albumin
CN103252218A (en) * 2013-04-26 2013-08-21 浙江工业大学 Hybrid overall crystal gel medium and preparation method thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106632860A (en) * 2016-12-23 2017-05-10 浙江工业大学 Glucosan-based cryogel microsphere separating medium and preparation method thereof
CN106632860B (en) * 2016-12-23 2019-05-24 浙江工业大学 A kind of glucan base crystalline substance glue microballoon separating medium and preparation method thereof
CN107141403A (en) * 2017-05-16 2017-09-08 齐鲁工业大学 A kind of Cu2+Chelate the preparation method of polyhydroxypropyl methaciylate super-macroporous crystal gel medium

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